Resinates from monomer

ABSTRACT

Reduced-rosin compositions of printing inks and the resinate binders therein, and the processes of preparation thereof, are described. In said compositions, a portion of the rosin normally used in the art is replaced by Monomer, and is further reacted with α,β-unsaturated carboxylic compound, alkaline metal salt, and solvent to produce the resinate binder product. Said resinate binder may then be formulated with a colorant to produce an ink, preferably for use in publication gravure.

This application is a continuation of U.S. application Ser. No.10/402,348, filed on Mar. 28, 2003, now U.S. Pat. No. 6,875,842 whichclaims benefit of provisional application No. 60/369,106, filed Mar. 28,2002.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to metal resinates, more specifically toresinates prepared from rosin and Monomer, and to the use of suchresinates in inks and coatings, particularly inks for gravure printing.

2. Description of the Related Art

The use of rosin as a major component of the reactants used to preparedbinders in printing inks is very well known in the art. Such rosin-basedinks are used for a wide variety of printing processes, includingflexography, gravure printing, letterpress printing, and lithography.Each printing process requires an ink with properties specific foroptimal usage of that particular process, where relevant ink propertiesinclude viscosity, solvent evaporation, wettability, pigment dispersion,and compatibility with the other materials composing the ink press. Inorder to be able to use rosin in inks having such a diverse range ofnecessary performance properties, it is very important to select theappropriate materials that are reacted with the rosin to form the inkbinder. See, e.g., Roger F. Burke, “Rosin-based Printing Inks,” NavalStores, Chapter 19, Pulp Chemicals Association (1989). Examples ofrosin-based inks in the art are summarized below.

U.S. Pat. No. 5,708,078 (Bender et al., 1998) discloses a resin and theprocess of preparation thereof, where said resin is formed from naturalresin and/or natural-resin acid, aldehyde and/or aldehyde acetal,polyhydric alcohol, and metal salt. Optionally, said resin may alsocomprise α,β-unsaturated carboxylic compound, animal- orvegetable-derived fatty acid and/or fatty acid ester, and/orethylenically unsaturated hydrocarbon resin. Among the objects of saidinvention are to provide a phenol-free ink composition, and to provide abinder resin imparting high ink gloss on printed material regardless ofprocessing speed.

U.S. Pat. No. 5,698,668 (Bender, 1997) discloses modified natural-resinester and the process of preparation thereof, wherein said resin estercomprises the reaction product of natural resin and/or natural-resinacid, α,β-unsaturated carboxylic compound, polyoxophenol compound,aldehyde and/or aldehyde acetal, polyhydric alcohol, metal salt, anddicarboxylic compound not ethylenically unsaturated, optionally animal-or vegetable-derived fatty acid and/or fatty acid ester, optionallyaromatic vinyl compound, and optionally polymer or oligomer of alkene.Among the objects of said invention are to provide a binder resinsuitable for use in gravure printing of illustrations.

U.S. Pat. No. 5,082,497 (LeVine, 1992) discloses printing ink and rosinresinate compositions comprising the reaction product of rosin,α,β-unsaturated carboxylic compound, metal salts of calcium or zinc anda Group I metal, and hydrocarbon solvent. An object of said invention isto provide improved resinates and gravure printing inks with theinclusion of a reactive Group I metal compound.

U.S. Pat. No. 4,301,055 (Schefbauer, 1981) discloses a calcium resinateand a printing ink composition containing said resinate, wherein saidresinate comprises the reaction product of calcium hydroxide, rosin,reactive hydrocarbon resin, polyanhydride of α-olefin-maleic anhydride,and optionally non-reactive hydrocarbon resin. Optionally, said rosin istall oil, wood, gum, polymerized, and/or polycyclopentadiene-tall oilrosin. An object of said invention is to provide a high melting calciumresinate that will be soluble in hydrocarbon solvents typically employedin printing inks.

U.S. Pat. No. 4,244,866 (Schefbauer, 1981) discloses a printing inkcomprising a resinate in a hydrocarbon solvent and a method of resinatepreparation thereof, said resinate comprising the reaction product ofrosin, calcium hydroxide, and polycarboxylic acid derived from maleicanhydride/α-olefin copolymer. Optionally, the rosin used in thepreparation of said binder is tall oil rosin. An object of saidinvention is to provide a high melting calcium resinate that will besoluble in hydrocarbon solvents typically employed in printing inks.

U.S. Pat. No. 4,079,102 (Wagner et al., 1978) discloses a printing inkcomposition comprising a binder comprising the reaction product ofcycloaliphatic diene resin and olefinically unsaturated polycarboxylicacid, optionally an olefinically unsaturated monocarboxylic acidcomponent selected from C₃₋₁₂ monocarboxylic acid and functionalderivatives of said monocarboxylic acid, optionally a monohydric orpolyhydric phenol component, and optionally a metal salt derived from ametal of Groups I-III of the Periodic Table. An object of said inventionis to provide a binding agent suitable for use in gravure printing.

BRIEF SUMMARY OF THE INVENTION

The increasingly popular use of rosin in applications other thanprinting inks has increased competition for an essentially fixed amountof rosin, and increased the incentive to find alternatives to rosin foruse in printing inks and binders therein. Therefore, an object of thepresent invention is to provide resinate binders for publication gravurethat are equal or superior in performance to those in commerce today butat a substantially lower cost. The present invention recognizes thatMonomer may be used in lieu of some of the rosin typically used inresinate production. This Monomer provides a lower cost alternative torosin acids, and can surprisingly improve certain performance propertiesof the ink that incorporates the Monomer.

In one aspect, the present invention provides a resinate compositioncomprising the reaction product of rosin, Monomer, and alkaline metalsalt wherein the cation of said salt is selected from Group IIA or GroupIIB of the Periodic Table. The composition may optionally include anα,β-unsaturated carboxylic compound, and/or an organic aromatic solvent,e.g., toluene, xylenes, and mixtures of aromatic solvents. In oneaspect, the composition comprises the reaction product of about 5-85 wt% rosin, about 1-50 wt % Monomer, about 1-25 wt % α,β-unsaturatedcarboxylic compound, about 1-15 wt % alkaline metal salt, and furtherincludes up to about 80 wt % solvent. Exemplary suitable rosins includewood rosin, gum rosin, and tall oil rosin (TOR). Exemplaryα,β-unsaturated carboxylic compounds are maleic anhydride, fumaric acid,mono (C₁-C₁₂alkyl) ester of fumaric acid, di(C₁-C₁₂alkyl) ester offumaric acid, acrylic acid, C₁-C₁₂alkyl ester of acrylic acid,methacrylic acid, C₁-C₁₂alkyl ester of methacrylic acid, itaconic acid,and C₁-C₁₂alkyl ester of itaconic acid, while a preferredα,β-unsaturated carboxylic compound is maleic anhydride. Exemplary metalcations of the alkaline metal salt are zinc, magnesium, and calcium.Exemplary anions of the alkaline metal salt are acetate, carbonate,bicarbonate, formate, hydroxide, oxalate and oxide. A preferred alkalinemetal salt is selected from calcium oxide, calcium hydroxide, magnesiumoxide, magnesium hydroxide, or a mixture thereof.

In one aspect, about 55-1% of the combined fatty acid and rosin acidequivalents are contributed by Monomer. In another aspect, about 35-10%of the combined fatty acid and rosin acid equivalents are contributed byMonomer. In another aspect, the acid equivalent ratio of rosin:Monomerin the reaction mixture used to form the resinate composition is about0.5:1 to 15:1. In another aspect, the acid equivalent ratio ofrosin:Monomer in the reaction mixture used to form the resinatecomposition is about 1:1 to 5:1. In one aspect, the composition furthercomprises water and an organic solvent selected from lower organic acid,hydrocarbon, or mixtures thereof. For example, in one aspect, thecomposition includes solvent where the solvent is composed of up toabout 15 wt % water, up to about 15 wt % lower organic acid, and about70-100 wt % hydrocarbon.

In a related aspect, the present invention provides a process forpreparing a resinate composition. The process comprises: (a) meltingrosin in a reaction vessel, optionally in admixture with Monomer; (b)further charging the reaction vessel with Monomer if Monomer is notalready present in the reaction vessel; (c) further charging thereaction vessel with alkaline metal salt wherein the cation of said saltis selected from Group IIA or Group IIB of the Periodic Table, andoptionally solvent, to provide a reaction mixture; (d) incubating thereaction mixture at elevated temperature to produce a reaction product;(e) heating the reaction product to evaporate excess solvent; and (f)cooling the reaction product (e) to yield a resinate composition. In oneaspect, the composition comprises the reaction product of about 5-85 wt% rosin, about 1-50 wt % Monomer, about 1-25 wt % α,β-unsaturatedcarboxylic compound, about 1-15 wt % alkaline metal salt, and optionallyup to about 80 wt % solvent.

For example, the present invention provides a process comprising (a)melting the rosin in a reaction vessel at about 170° C., optionally inadmixture with Monomer; (b) charging the reaction vessel with Monomer ifMonomer is not already present in the reaction vessel, and optionallyα,β-unsaturated carboxylic compound; (c) heating the reaction mixture atabout 225° C. for about 1 hour; (d) cooling the reaction mixture to lessthan about 100° C., preferably about 80-100° C.; (e) charging thereaction vessel with one or more of lower organic acid, water andhydrocarbon; (f) charging the reaction vessel with a slurry comprisinghydrocarbon solvent, alkaline metal salt, and optionally tall oil fattyacid; (g) incubating the reaction mixture at less than about 100° C. forabout 30 minutes; (h) heating the reaction mixture at about 115° C. forabout 1-2 hours; and (i) cooling and discharging said reaction mixture.As another example, the present invention provides a process ofpreparing a resinate composition by a fusion method, in one aspectcomprising the ordered steps of (a) melting the rosin in a reactionvessel at about 170° C., optionally in admixture with Monomer; (b)charging the reaction vessel with Monomer if Monomer is not alreadypresent in the reaction vessel, and optionally α,β-unsaturatedcarboxylic compound; (c) heating the reaction mixture at about 200° C.for about 1 hour; (d) charging the reaction vessel with a slurrycomprising hydrocarbon solvent, alkaline metal salt, and optionally talloil fatty acid; (e) incubating the reaction mixture about 250° C. forabout 90 minutes; (f) charging the reaction vessel with lower organicacid; and (g) further incubating the reaction mixture for about 1 hourbefore cooling and discharging the final reaction mixture. In oneaspect, the composition comprises the fusion method reaction product ofabout 20-85 wt % rosin, about 1-50 wt % Monomer, about 1-25 wt %α,β-unsaturated carboxylic compound, about 1-15 wt % alkaline metalsalt, up to about 30 wt % hydrocarbon solvent, up to about 5 wt % lowerorganic acid, and optionally up to about 5 wt % water.

In one aspect, the present invention provides a modification of anyresinate manufacturing process known in the art, the modification beingthat up to about 55 acid equivalent percent of the rosin is substitutedwith Monomer. In related aspects the present invention provides printingink comprising pigment and the resinate binder as summarized above. Thepresent invention also provides a process for preparing a printing inkthat includes preparing a resinate binder as summarized above and thencombining that resinate binder with a pigment. In preferred aspects, theprinting ink is formulated for gravure printing. The present inventionalso provides varnishes that include the resinate binder as describedabove, where these varnishes may be combined with pigment to form aprinting ink.

These and other aspects of this invention will become apparent uponreference to the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides for the preparation of a cost-effectiveresinate material for use in printing inks. It is well-known to thoseexperienced in the art that natural rosins and rosin acids normallyutilized in the production of printing inks are a relatively expensivecomponent of the ink binder, and furthermore rosin is in increasinglyshort global supply. The present invention succeeds in finding asuitable replacement for some of this rosin as used in resinateproduction, and furthermore provides inks that have equal or superiorperformance properties to the inks that do not include the replacementfound according to the present invention.

In one aspect, the present invention provides a composition forpreparing a resinate, the composition comprising rosin, Monomer, andalkaline metal salt. Each of these components will now be described.Rosin is mainly a mixture of C₂₀, tricyclic fused-ring, monocarboxylicacids, typified by abietic acid. Individually, these monocarboxylicacids are commonly referred to as resin acids. Rosin can be obtainedfrom many sources, and can have a wide range of purities. For example,wood rosin may be employed in the invention, where wood rosin isobtained from Pinus stumps after harvesting the stumps, chipping thestumps into small chips, extracting the chips with hexane orhigher-boiling paraffins, and distilling the hexane or paraffin andfatty acids to yield wood rosin. Gum rosin, which is the name given torosin that is obtained after scoring a pine tree, collecting the exudatesap, and then distilling away the volatile components and most of thefatty acids, may also be employed in the invention.

The Kraft wood pulping process, also known as the sulfate pulpingprocess, produces tall oil as a byproduct of the paper-making process.According to this process, pinewood is digested with alkali and sulfide,producing tall oil soap and crude sulfate turpentine as by-products.Acidification of this soap followed by fractionation of the crude talloil yields rosin and fatty acid as two of the major components. Therosin obtained by this process is known as tall oil rosin (TOR) and thefatty acid obtained by this process is known as tall oil fatty acid(TOFA). Rosin is typically characterized by its acid number, and rosinshaving acid numbers ranging from about 160 to about 180 are preferredaccording to the invention. Preferably, the tall oil rosin has undergonedistillation so as to have less than about 5 weight percent tall oilfatty acids. A preferred rosin is available commercially from ArizonaChemical Company, Jacksonville, Fla., under the SYLVAROS® trademark. Invarious aspects, the resinate composition of the present inventioncomprises, or is prepared from reactants that comprise about 5-85 wt %,15-85 wt %, 25-85 wt %, 35-85 wt %, 45-85 wt %, 55-85 wt %, 65-85 wt %,or 75-85 wt %; or about 5-75 wt %, 15-75 wt %, 25-75 wt %, 35-75 wt %,45-75 wt %, 55-75 wt %, or 65-75 wt %; or about 5-65 wt %, 15-65 wt %,25-65 wt %, 35-65 wt %, 45-65 wt %, or 55-65 wt %; or about 5-55 wt %,15-55 wt %, 25-55 wt %, 35-55 wt %, or 45-55 wt %; or about 545 wt %,1545 wt %, 2545 wt %, or 3545 wt %; or about 5-35 wt %, 15-35 wt %, or25-35 wt %; or about 5-25 wt %, or 15-25 wt %; or about 5-15 wt % rosin.In preferred aspects of the present invention, the resinate compositioncomprises, or is prepared from reactants that comprise, 5-80 wt % rosin,more preferably 10-75 wt % rosin, even more preferably 15-70 wt % rosin.In one aspect, the rosin used in the resinate composition of the presentinvention is selected from the group consisting of tall oil rosin, gumrosin, and a combination thereof. In further various aspects, the rosinof the composition, or the rosin used to prepare the composition,comprises about 0-100 wt %, 10-100 wt %, 20-100 wt %, 30-100 wt %, or35-100 wt %; or about 0-90 wt %, 10-90 wt %, 20-90 wt %, 30-90 wt %, or35-90 wt %; or about 0-80 wt %, 10-80 wt %, 20-80 wt %, 30-80 wt %, or35-80 wt %; or about 0-75 wt %, 10-75 wt %, 20-75 wt %, 30-75 wt %, or35-75 wt %; or about 0-65 wt %, 10-65 wt %, 20-65 wt %, 30-65 wt %, or35-65 wt % tall oil rosin, while in a preferred aspect the remainder ofthe rosin comprises gum rosin.

As mentioned previously, a co-product of rosin production is TOFA. TOFAis composed mainly of C₁₆₋₁₈ carboxylic acids, which are largelyunsaturated in their acyl chain structure. Exemplary tall oil fattyacids include unsaturated acids such as oleic acid, oleic acid isomers,linoleic acid, and linoleic acid isomers, as well as small percentagesof saturated fatty acid such as stearic acid. Due to its high content ofunsaturated fatty acid, TOFA may be, and commonly is subjected to acidicclay catalyzed polymerization. In this polymerization process, which istypically conducted at high temperatures, the olefinic fatty acidsundergo intermolecular addition reactions, by, e.g., the ene-reaction,so as to form polymerized fatty acid. The mechanism of this reaction isvery complex and incompletely understood at the present time. However,for purposes of the present invention it will suffice to note that theproduct of this polymerization process comprises, in large part,dimerized fatty acid and a unique mixture of monomeric fatty acids. Thispolymerization product is commercially subjected to distillation inorder to provide a fraction highly enriched in dimerized fatty acid,which is commonly known in the art as “dimer acid” or “dimer fattyacid”. This distillation process will also provide a fraction that ishighly enriched in the monomeric fatty acids, where this fraction iscommonly known in the art as “monomer” or “monomer acid” or “monomerfatty acid”, and will be referred to herein as Monomer.

Monomer is a unique composition. Whereas the natural source-derived TOFAlargely consists of linear C₁₈ unsaturated carboxylic acids, principallyoleic and linoleic acids, Monomer contains relatively small amounts ofoleic and linoleic acids, and instead contains significant amounts ofbranched and cyclic C18 acids, both saturated and unsaturated, as wellas elaidic acid. The more diverse and significantly branched compositionof Monomer results from the thermal catalytic processing carried out onTOFA by the polymerization process just described. The art recognizesthat the reaction of Monomer with other chemical substances yieldsunique, identifiable derivative substances that are chemically differentfrom corresponding TOFA derivatives. Monomer has been assigned CASRegistry Number 68955-98-6. A suitable Monomer for the practice of thepresent invention is “MO6” as available from Arizona Chemical Company,Jacksonville, Fla.

As mentioned above, the present invention recognizes that some of therosin normally present in a resinate composition may be replaced withMonomer. Surprisingly, the resulting resinate composition can perform atleast adequately in a printing process. Even more surprisingly, someimprovements in performance properties have been observed. For example,the Monomer-containing resinate compositions of the present inventionhave shown some improvement in the solvent release properties of theink. In addition, the blocking properties of the printed substrate showsome improvement when Monomer has been used to form the resinatecomposition.

In an alternative aspect of the present invention, some of the rosinused in a resinate-forming reaction is replaced with fatty acid, wherethat fatty acid is not necessarily Monomer. In various embodiments,5-10%, or 11-15%, or 16-20%, or 21-25%, or 26-30%, or 31-35%, or 36-40%,or 41-45%, or 46-50% of the acid equivalents in a resinate-formingreaction are contributed by fatty acid, where that fatty acid isoptionally Monomer or TOFA or a mixture thereof. While in preferredembodiments discussed extensively herein, the fatty acid is, orcomprises, Monomer, in other embodiments the fatty acid is, or comprisesTOFA. In another aspect, the fatty acid is, or comprises,vegetable-derived fatty acid. Thus, in one aspect of the presentinvention, the Monomer as described herein is replaced in whole or partwith TOFA. For example, the present invention provides a resinatecomposition comprising the reaction product of reactants, the reactantscomprising: (a) rosin; (b) TOFA; and (c) metal salt, the metal saltcomprising a metal cation, the metal selected from Group IIA or GroupIIB metals of the Periodic Table; where, in various embodiments, 5-10%,or 11-15%, or 16-20%, or 21-25%, or 26-30%, or 31-35%, or 36-40%, or41-45%, or 45-50% of the acid equivalents attributed to acid-containingreactants are contributed by the TOFA.

However, in a preferred aspect of the present invention, a resinate isprovided that is prepared from a mixture including rosin, preferablyincluding tall oil rosin, and Monomer. In another aspect, up to about 55acid % of the rosin in an otherwise standard resinate composition isreplaced with Monomer. Thus, in various aspects, the present inventionprovides resinate compositions wherein about 55-1%, 50-1%, 45-1%, 40-1%,35-1%, 30-1%, 25-1%, 20-1%, 15-1%, or 10-1%; or about 55-5%, 50-5%,45-5%, 40-5%, 35-5%, 30-5%, 25-5%, 20-5%, 15-5%, or 10-5%; or about55-10%, 50-10%, 45-10%, 40-10%, 35-10%, 30-10%, 25-10%, 20-10%, or15-10%; or about 55-15%, 50-15%, 45-15%, 40-15%, 35-15%, 30-15%, 25-15%,or 20-15%; or about 55-20%, 50-20%, 45-20%, 40-20%, 35-20%, 30-20%, or25-20%, of the combined rosin and fatty acid acid equivalents may becontributed by Monomer. In a preferred aspect, about 35-10% of thecombined rosin and fatty acid acid equivalents are contributed byMonomer, because this amount provides a composition with satisfactoryperformance properties and relatively low cost. In the followingdiscussion, an amount of 35-10% is typically disclosed, however otheramounts as set forth above may also be used. In other aspects of thepresent invention, the acid equivalent ratio of rosin:Monomer in theresinate composition may be about 0.5:1 to 15:1, 0.5:1 to 10:1, or 0.5:1to 5:1; or about 0.75:1 to 15:1, 0.75:1 to 10:1, or 0.75:1 to 5:1; orabout 1:1 to 15:1, 1:1 to 10:1, or 1:1 to 5:1. In a preferred aspect,the acid equivalent ratio of rosin:Monomer in the resinate compositionis about 1:1 to 5:1, and this provides a composition with satisfactoryperformance and relatively low cost.

In another aspect, the resinate composition of the present inventioncomprises an alkaline metal salt. As used herein, the term “resinate”refers to a rosin, which is a carboxylic acid-containing material, inthe form of a salt, i.e., a carboxylic acid salt. Also used herein, theterm “alkaline metal salt” refers to an ionic compound containing ametal cation and an inorganic or lower organic anion, which compoundtends to increase the alkalinity of the solution into which it isdissolved. Thus, in one aspect of the present invention, alkaline metalsalt is combined with rosin and Monomer, which reacts withmonocarboxylic acid moieties present in the acid components of thereaction mixture to produce metal carboxylate functionalities. Suchtreatment renders the resulting resinate composition readily soluble inorganic solvent. In the present invention, the cation of the alkalinemetal salt is preferably divalent (i.e., carries a charge of +2), morepreferably selected from the elements of Group IIA or Group IIB or thePeriodic Table (e.g., Be, Mg, Ca, Sr, Ba, Zn, or Cd). Rosin salts ofdivalent cations of zinc, magnesium, and calcium have particularly goodpigment wetting properties, and are even more preferred in the resinatesof the present invention. Most preferably, the cation of the alkalinemetal salt is divalent calcium or magnesium cation. Said salts may bethe acetate, carbonate, bicarbonate, formate, hydroxide, oxalate oroxide of a metal. Calcium and magnesium salts (including withoutlimitation, calcium oxide, calcium hydroxide, magnesium oxide, andmagnesium hydroxide) are further preferred. In one aspect of the presentinvention, the resinate composition comprises about 1-15 wt %, 2-15 wt%, or 3-15 wt %; or about 1-12 wt %, 2-12 wt %, or 3-12 wt %; or about1-10 wt %, 2-10 wt %, or 3-10 wt % alkaline metal salt, preferably 3-10wt % alkaline metal salt.

The resinate compositions of the present invention may also, but neednot, contain one or more α,β-unsaturated carboxyl compounds or estersthereof. An α,β-unsaturated carboxyl compound has an olefinicunsaturation adjacent to the carbon atom of a carboxyl group, i.e., hasthe —C═C—C(═O)—O-arrangement of carbon and oxygen atoms. Theα,β-unsaturated carboxyl compound is reactive with rosin and tall oilpitch, to form an adduct therebetween. When the α,β-unsaturated carboxylcompound is maleic anhydride, the adduct between rosin and maleic acidis known as maleated rosin. When the α,β-unsaturated carboxyl compoundis fumaric acid, or an ester of fumaric acid, then the correspondingadduct formed between rosin and fumaric acid or a fumarate is known asfumarated rosin. When the α,β-unsaturated carboxyl compound reacts withtall oil pitch, the reaction product is known as maleated pitch (whenmaleic anhydride is the α,β-unsaturated carboxyl compound) or fumaratedpitch (when fumaric acid or an ester thereof is the α,β-unsaturatedcarboxyl compound).

Suitable α,β-unsaturated carboxylic compounds include maleic anhydride,fumaric acid, mono (C₁-C₁₂alkyl) ester of fumaric acid, di(C₁-C₁₂alkyl)ester of fumaric acid, acrylic acid, C₁-C₁₂alkyl ester of acrylic acid,methacrylic acid, C₁-C₁₂alkyl ester of methacrylic acid, itaconic acid,and C₁-C₁₂alkyl ester of itaconic acid. Maleic anhydride, fumaric acidand esters of fumaric acid are preferred α,β-unsaturated carboxyliccompounds, with maleic anhydride being most preferred. In variousaspects of the present invention, the resinate composition comprisesabout 1-25 wt %, 2-25 wt %, or 3-25 wt %; or about 1-20 wt %, 2-20 wt %,or 3-20 wt %; or about 1-15 wt %, 2-15 wt %, or 3-15 wt % maleicanhydride, preferably 3-15 wt % maleic anhydride.

The resinate compositions of the present invention may also, but neednot, contain TOFA. In various aspects, the resinate composition of theinvention comprises about 0.01-2 wt %, 0.01-1.5 wt %, 0.01-1 wt %, or0.01-0.5 wt %; or about 0.02-2 wt %, 0.02-1.5 wt %, 0.02-1 wt %, or0.02-0.5 wt %; or about 0.03-2 wt %, 0.03-1.5 wt %, 0.03-1 wt %, or0.03-0.5 wt % tall oil fatty acid, preferably 0.02-1 wt % tall oil fattyacid, more preferably 0.03-0.5 wt % tall oil fatty acid. The fatty acidis primarily used to disperse alkaline metal salts in solvent. Fattyacids other than TOFA, for example the fatty acids present in Monomer,can be used for this same purpose.

The resinate compositions of the present invention may also, but neednot, contain phenolic compound(s). Phenolic compounds suitable for useas a component of the resin-forming composition of the inventioninclude, without limitation, phenol, C₁₋₁₂ alkylphenols, arylphenols,aralkylphenols, cresols, 1,3,5-xylenols, diphenylolpropane, cumylphenol,and the like. As used herein, alkyl refers to a hydrocarbon structuraldomain containing exclusively C—C and C—H single bonds; aryl refers to ahydrocarbon structural domain as an aromatic ring system; while aralkylrefers to a hydrocarbon structural domain containing both aromatic andalkyl moieties. In various aspects of the present invention, phenoliccompound is 0-50%, 0-40%, or 0-30% of the total weight of theresinate-forming components, and is preferably 0-25% of the total weightof the resinate-forming components. In additional aspects of theinvention, for each of these percentage ranges, phenol may constitute0-100% of the phenolic compound.

The resinate compositions of the present invention may also, but neednot, contain aldehyde. The aldehyde of the present invention is reactivewith rosin and phenol, to produce crosslinked resinous adducts.Exemplary aldehydes of the present invention include, withoutlimitation, formaldehyde, paraformaldehyde, acetaldehyde,glyceraldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde, furfural,and glyoxal. In various aspects of the present invention, aldehyde is0-40%, 0-30%, or 0-20% of the total weight of the components used toform the resinate composition of the present invention, and ispreferably 0-15% of the total weight of the resinate-forming components.Paraformaldehyde is a preferred aldehyde to be used as a resin-formingcomponent, and the term “formaldehyde” is used herein to include bothformaldehyde and paraformaldehyde.

In an optional aspect, the phenolic compound is pre-reacted with thealdehyde, so as to provide a so-called phenolic resin. Thus, phenoliccompound and aldehyde may be added to the resin-forming reaction mixturein the form of a phenolic resin, rather than, or in addition to, the twoindividual reactants.

The resinate compositions of the present invention may also, but neednot, contain polyhydric alcohol. Polyhydric alcohols of the presentinvention are reactive with acidic moieties via standard esterificationreactions, and are reactive with ester moieties via standardtransesterification reactions, to produce crosslinked resinous adducts.Exemplary polyols include, without limitation, alkylene glycol (such asethylene glycol and propylene glycol), polyalkylene glycol (such aspolyethylene glycol and polypropylene glycol), alkylene triol (such asglycerol, trimethylolethane, and trimethylolpropane), tetrafunctionalalcohols such as pentaerythritol, pentafunctional alcohols such asdimerized trimethylolpropane, or hexafunctional alcohols such asdimerized pentaerythritol, where a preferred polyol of the presentinvention is pentaerythritol. In various aspects of the presentinvention, polyhydric alcohol is 0-25%, 0-20%, or 0-15% of the totalweight of the components used to form the resinate composition of thepresent invention, and is preferably 0-15% of the total weight of theresinate-forming components.

In another aspect, the resinate composition of the present inventioncomprises solvent. The solvent is not, however, a resin-forming reactantor component. In other words, while the solvent may be part of thecomposition, the solvent is not considered to be a reactant. The weightpercent values provided herein that describe reactant amounts do notconsider whether any solvent is present, i.e., these weight percentvalues are based on the total weight of the reactants. However, whendiscussing the composition of the invention, which may include resinateand solvent, weight percent values based on the total weight of thecomposition may be provided herein when discussing the weight of solventand/or the weight of resinate in the composition.

The solvent is composed of one or more solid or liquid components. In apreferred aspect, the solvent of the composition of the presentinvention is composed only of liquid components; more preferably, thesolvent comprises more than one liquid component. A preferred aspect ofthe composition of the present invention is one wherein the solvent iscomprised of at least one organic compound, wherein the term “organic”as used herein refers to a compound having a molecular structurecontaining at least one carbon atom. Conversely, an inorganic compoundis one having a molecular structure containing no carbon atoms.According to one aspect of the present invention, said organiccompound(s) is(are) preferably free of hydroxyl, aldehyde, alkenyl,cycloalkenyl, and nitrogen-containing groups. As used herein, alkenylrefers to a hydrocarbon structural domain containing at least one C═Cdouble bond, while cycloalkenyl refers to an alkenyl structural domainconfigured in a cyclic orientation. Though it is typical in the art toinclude alcohol and aldehyde-containing compounds in the reactionmixtures of resins and resinates (e.g., optionally-substituted phenolsand formaldehyde), certain of these compounds may be hazardous to humansupon exposure in large quantities, such as may be encountered during theprocess of manufacture. Therefore, in one aspect, the present inventionprovides for compositions that avoid use of these hazardous materials.In a preferred aspect, the resinate composition of the present inventioncomprises up to about 80 wt %, more preferably up to about 70 wt %, evenmore preferably up to about 60 wt %, solvent.

Exemplary organic solvent components according to the present inventioninclude lower organic acid (exemplified by, without limitation, aceticacid) and hydrocarbons, wherein said hydrocarbons may be alkyl, aryl, oraralkyl. In a preferred aspect, the hydrocarbon of the solvent of thepresent invention is selected from the group consisting of xylene andtoluene. In a further preferred aspect, the solvent of the presentinvention is selected from the group consisting of lower organic acid,hydrocarbon, water, and mixtures thereof, preferably a compositionconsisting of about 70-100 wt % hydrocarbon, up to about 15 wt % lowerorganic acid, and optionally up to about 15 wt % water.

The present invention also provides a process for preparing a resinatecomposition, where the process comprises forming a fluid mixturecomprising rosin, Monomer, alkaline metal salt, solvent, and anyoptional components such as α,β-unsaturated carboxylic compound;reacting together the components of this mixture to produce a reactionproduct; optionally heating the reaction product to evaporate excesssolvent; and cooling the reaction product to yield a resinatecomposition. The rosin, Monomer, alkaline metal salt, solvent, and anyoptional components may be added together in any order. In a preferredprocess, the rosin is melted and then the other components are added tothe molten rosin; however in one aspect, phenol compound may be chargedto the reaction vessel before or during rosin melting. In anotherpreferred aspect, the rosin and Monomer are added to a reaction vesseland these two components are heated to achieve a homogeneous moltenstate.

As used herein, the term “reacting together” means that each of therequired and optional components is added to a reaction vessel underreaction conditions such that each component reacts with either a)another component, or b) a reaction product formed from two or moreother reaction components. In order for the components to undergo aresinate-forming reaction, combinations of the components must beexposed to an elevated temperature in the range of 80-300° C. At theseelevated temperatures, the components undergo covalent and ionicbond-forming reactions with other components, so that some increasedmolecular weight material is formed.

For example, each of the components may be combined in a single reactionvessel, and the combination taken to elevated temperature so that thecomponents react with one another to form a resinate of the invention.This approach may be termed a “one-pot” reaction process. Alternatively,two or more (but less than all) components may be combined in a singlereaction vessel, and this combination taken to elevated temperature sothat the components react with one another to form an intermediatereaction product. Then other components are reacted with theintermediate reaction product. For example, in the present invention therosin and Monomer may be combined and heated, a process by which therosin component will melt. The resulting reaction mixture can then becombined with the other reaction components (in this invention, alkalinemetal salt, solvent, and optional components such as tall oil fatty acidand α,β-unsaturated carboxylic compound). Preferably the rosin andMonomer are combined prior to introduction of alkaline metal salt, tohelp maximize the formation of carboxylate functionalities in theresinate composition. The combination is then taken to elevatedtemperature, typically between 50° C. and 300° C., preferably 80° C. to250° C., under either normal (atmospheric) pressure or elevated pressureas may be achieved in, e.g., an autoclave.

The present invention also provides that after reacting togethercomponents in a reaction mixture, an additional amount of one or more ofsaid components may be added to the reaction mixture and further reactedtogether. This is commonly done in commercial resinate production, andis illustrated in the Examples provided herein. It should be recognizedthat the same components (in terms of quantity and identity) may formresinates with different properties, depending on the precise manner inwhich the components are reacted together. However, determining theseproperties is well within the skill of the ordinary artisan.

The reaction temperature(s) is selected with the following points inmind. The reaction temperature must be high enough that the contents ofthe reaction vessel are sufficiently fluid to allow those contents to bestirred. Higher temperatures are generally preferred for reasons ofeconomy, in order to provide a faster rate of reaction. However, thereaction temperature should not be so great that the reaction componentsboil out of the reaction vessel. Nor should the temperature be so greatthat decomposition of the reaction components or reaction productsshould occur.

The resinate-forming reaction generates water as a byproduct of thebonds that are formed between members of the reaction components. Inorder to drive the reaction toward completion, this water should beremoved from the reaction or product mixture. In the absence of vacuumor azeotrope formation, a reaction temperature of at least 100° C. isneeded in order to distill water away from the reacting components.Thus, at least during the initial stage(s) of resinate formation, thereaction temperature is desirably set to about 100-125° C. While ahigher initial reaction temperature may be used, the consequence may bewater generation at a rate that is much greater than water removal maybe conveniently accomplished.

In order to drive the reaction to completion, removal of water may beenhanced through addition of an organic solvent that forms a low-boilingazeotrope with water, and/or the addition of a light vacuum on thereaction vessel. To provide a low-boiling azeotrope, an organic solventthat forms an azeotrope with water, e.g., toluene or xylene, can beadded to the reaction vessel, and then removed by distillation, undernormal pressure. If the final product form is a solution, the samesolvent is the azeotroping agent.

The reaction components are maintained at about 100-300° C. until thereaction is considered finished. Reaction progress is convenientlymonitored by periodically taking samples of the reaction mixture andmeasuring one or more relevant properties of the sample. For example,initially the acid number of the reaction mixture may be as high asabout 300. The acid number will gradually fall as the resinate-formingreaction proceeds. Melting point (softening point), melt viscosity,and/or solution viscosity measurements may also be made to monitorreaction progress.

In one preferred embodiment of the present invention, the process forpreparing a resinate composition comprises the ordered steps of: (a)melting the rosin in a reaction vessel at about 170° C., optionally inadmixture with Monomer; (b) charging the reaction vessel with Monomer ifMonomer is not already present in the reaction vessel, and optionallyα,β-unsaturated carboxylic compound; (c) heating the reaction mixture atabout 225° C. for about 1 hour; (d) cooling the reaction mixture to lessthan about 100° C.; (e) charging the reaction vessel with one or more oflower organic acid, water and hydrocarbon; (f) charging the reactionvessel with a slurry comprising hydrocarbon solvent, alkaline metalsalt, and optionally tall oil fatty acid; (g) incubating the reactionmixture at less than about 100° C. for about 30 minutes; and (h) heatingthe reaction mixture at about 115° C. for about 1-2 hours before coolingand discharging the reaction product. In utilizing this process, theresulting resinate composition preferably comprises about 20-80 wt %hydrocarbon solvent, more preferably about 30-70 wt % hydrocarbonsolvent, and even more preferably about 40-60 wt % hydrocarbon solvent.

In another embodiment of the present invention, the resinate compositionof the present invention is prepared by a process referred to as the“fusion method”. Explained briefly, a fusion method is a dry preparationprocess whereby components are combined in the absence of solvent, thereaction mixture is rendered molten and given time to react, and themixture is then cooled to yield a resinate product that is essentiallywater-free and solvent-free. In a method variation, the reaction mixturefurther comprises a small quantity of a hydrocarbon solvent, preferablytoluene or xylene, in order to remove water from the mixture uponheating, via azeotropic distillation. Thus, with the fusion method ofresinate preparation, much less hydrocarbon solvent is used incomparison to other known methods of resinate preparation, allowing theskilled artisan to prepare resinate without the added reaction volumes,cost, and exposure hazards associated with solvent use.

In a preferred embodiment, the process for preparing a resinatecomposition comprises the ordered steps of: (a) melting the rosin in areaction vessel at about 170° C., optionally in admixture with Monomer;(b) charging the reaction vessel with Monomer if Monomer is not alreadypresent in the reaction vessel; (c) heating the reaction mixture atabout 200° C. for about 1 hour; (d) charging the reaction vessel with aslurry comprising hydrocarbon solvent and alkaline metal salt; (e)incubating the reaction mixture about 250° C. for about 90 minutes; (f)charging the reaction vessel with lower organic acid; and (g) furtherincubating the reaction mixture for about 1 hour before cooling anddischarging the final reaction product. In utilizing this process, theresinate composition preferably comprises up to about 30 wt %hydrocarbon solvent, more preferably up to about 25 wt % hydrocarbonsolvent, and even more preferably up to about 20 wt % hydrocarbonsolvent. In various other aspects of this process, α,β-unsaturatedcarboxylic compound may be added to the reaction mixture after rosinmelting and prior to heating; tall oil fatty acid may be included aspart of the slurry; phenolic compound may be charged to the reactionvessel before or during the rosin melting; aldehyde may be added to thereaction mixture after rosin melting and prior to heating; or polyhydricalcohol may be added to the reaction mixture after rosin melting andprior to cooling and discharge.

The resinates of the present invention may be characterized by theirproperties, which include acid number, melting point, viscosity, anddilutability in toluene. These properties are routinely measured forsuch resins and resinates, and thus one of ordinary skill in the art isvery familiar with techniques to measure these properties. Nevertheless,a brief description of techniques to measure certain of these propertiesis provided here.

Acid number is measured by dissolving a known weight of resin orresinate into an organic solvent (toluene is a typical solvent), andthen titrating a measured amount of methanolic potassium hydroxide (KOH)solution into the resin or resinate solution. The titration is completewhen a pH of about 7 is attained. The acid number of the resin orresinate is equal to the amount of KOH, in mg, which was used in thetitration, divided by the weight of resin or resinate, in grams, in thesample that was titrated. In other words, acid number is equal to the mgof KOH needed to neutralize 1 gram of sample.

Melting point, which may also be referred to as “softening point,” maybe measured by the so-called “ring and ball” method, which is thesubject of ASTM E28. Alternatively, a softening point value may beobtained using a Mettler FP80 Central Processor and a Mettler FP83 HTDropping Point Cell employing a softening point ring. This apparatus isavailable from Mettler Laboratories (Hightstown, N.J.). The meltingpoint values described and reported herein were obtained using either aMettler FP83HT apparatus or a ring and ball apparatus.

Viscosity is measured on resin or resinate solutions using Gardnerviscosity tubes compared to reference standards. In this test(hereinafter referred to as the “Gardner Holdt Bubble method”) a resinsolution is poured into a tube of standard (10.65 mm) internal diameterleaving a standard volume of air at the top of the tube. The tube iscorked and placed in a water bath at 25° C. Tubes filled with siliconeoil based standard of known viscosity are placed in a rack next to thetube with the resin solution of unknown viscosity. The tubes areinverted and the viscosity is determined relative to standard bycomparing the rate of rise of the bubbles created by the air space attop of the tubes. This so-called “bubble rise time” viscosity isreported by comparison to standards. The standards range from lowviscosity to high viscosity as follows: A3, A2, A1, A through Z, Z1through Z10. If the bubble of the unknown is between two of thereference standards it is reported as such. For example if the bubble ofthe unknown sample rises at a rate between the Z and Z1 tube, theviscosity is reported as Z-Z1.

Viscosity may also be measured using a Physica Viscolab LC3 viscometer,according to the method of ISO 3219 (“Plastics, polymers, resiris in theliquid state or as emulsions of dispersions—Determination of viscosityusing a rotational viscometer with defined shear rate”). Measurementsobtained by this method are typically reported in units of mPa·s. Thisviscometer is available from Physica Messtechnik GmbH, Stuttgart,Germany (www.physica.de).

Toluene dilution is measured by weighing a known quantity of resinatesolution and diluting it with toluene until print viscosity is achieved.Print viscosity is determined using a flow or efflux cup available froma number of manufacturers and standards organizations. Typical cups usedinclude the Shell #2 and DIN 3 mm cups, which both are designed to yieldthe viscosity of press ready ink at a particular flow time. The knownquantity of resinate solution is diluted to a standard flow time (e.g.,18 seconds on a Shell #2 cup or 25 seconds on a 3 mm DIN cup) at astandard temperature (typically 21° C. or 25° C.) and the amount oftoluene is recorded in either mLs or grams per sample size used. Forexample, if 75 mLs of toluene was required to reduce the viscosity of100 grams of resinate solution to achieve a flow rate of 18 seconds on aShell # 2 cup at 25° C., the toluene dilution would be reported as 75mLs toluene required to achieve print viscosity on a Shell #2 cup.

The present invention also provides an ink suitable for printing,preferably gravure printing. In gravure printing, a cylinder onto whichis engraved or etched the image to be printed is rolled directly intoink and transferred directly to the substrate that accepts the printedimage. This is in contrast to other forms of printing wherein ink istransferred by rolling onto one or several additional cylinders beforetransferring ink onto the substrate. Gravure printing is very commoncommercial mode of printing, and is well known to one of ordinary skillin the art. Gravure printing is often used in printing on substratessuch as magazine stock, metal foils, plastic films, and paper cartons.

A gravure ink of the present invention contains a resinate as disclosedherein, in addition to a solvent, a colorant and optionalperformance-enhancing additives. The inventive resinate can be usedalone or in combination with co-resins. Suitable co-resins includecommonly known co-resins such as, without limitation, rosin modifiedmaleic and phenolic esters, and hydrocarbon resins. Owing to the lack ofintermediary rollers and/or cylinders utilized in gravure printing, theink used in gravure printing must be of very low viscosity and finelyground so as to reduce the amount of scratching imparted to the engravedor etched cylinder; yet, because of the relative absence ofsolvent-sensitive (i.e., rubber-composed) moving parts needed for saidprinting process, a wide range of solvents are acceptable for use ingravure printing. Suitable solvents include, without limitation, mineraloils, aromatic and ester solvents. Suitable colorants include flushedcolor, dry pigments and soluble dyes. Additives can include, withoutlimitation, waxes, wetting agents, and plasticizers. In addition to thematerials noted above, the ink additionally may contain any number ofoptional components, where the optional component(s) provide forimprovements in the performance of the ink. Ink performance propertiesinclude color strength, gloss, scuff resistance, block resistance,misting, open time on press and many other properties.

Printing ink may be prepared by adding colorant (flush color, drypigment or soluble dyes), additives and additional solvent to a letdownvarnish comprising a resinate composition of the present invention.Flush color is a form of pigment where the solvent used during thepigment manufacturing process (water) has been replaced by a hydrocarbonor oil based varnish. Such a varnish can contain the inventive orconventional resins, resinates, or a combination of both. Finished inkmay be prepared by adding the flush color and the letdown varnish whilemixing at low shear. The mixture can be passed through a bead mill orshot mill to further reduce pigment particle size and improve final inkproperties. Soluble dyes can be added with little or no additionalenergy to impart color to the system. Additional varnish or solvent canbe added to adjust tack, flow and viscosity to reach targetspecifications and then additives are blended in.

One of ordinary skill in the art is familiar with preparing printinginks using either flush color, dry pigment or soluble dyes and may adoptother procedures for preparing such a printing ink.

The invention is illustrated in more detail by the following examples.In the following examples, chemicals were of reagent grade unless notedotherwise, and were obtained from commercial supply houses such asAldrich Chemical Co. (Milwaukee, Wis.). MERIGRAL™ HV modified resinatewas obtained from DRT (DAX Cedex, France). SYLVAROS™ 85 tall oil rosin,SYLVAROS™ NCY tall oil rosin, and SYLVAPRINT™ GS62126 T37 resinate wereobtained from Arizona Chemical (Jacksonville, Fla.). MO6 monomer fattyacid is Monomer as obtained from Arizona Chemical (Jacksonville, Fla.).HRJ 1367 para-tert-butylphenol/formaldehyde phenolic resin was obtainedby Schenectady International (Schenectady, N.Y.). Comparative examplesare denoted by the example number followed by the letter “C”.

EXAMPLES Example 1 Solution Resinate with 30 Percent of Acid fromMonomer

A reaction vessel was charged with tall oil rosin, and said rosin wasmelted at 170° C. Then, said reaction vessel was further charged withMO6 fatty acid monomer and maleic anhydride, and heated at 225° C. for60 min. The resulting adduct was cooled to 160° C., before furthercharging said reaction vessel with toluene. The mixture temperature wasadjusted to 92° C., before further charging said reaction vessel withacetic acid and water, followed by a slurry of toluene, tall oil fattyacid and calcium hydroxide. The mixture was held at 92° C. for 30minutes, then heated to about 100° C. until nearly all water had beendistilled from the reaction mixture. Percent composition (by mass) ofthe total reaction mixture is indicated in Table 1.

Following removal of water from the reaction mixture, viscosity andsolids were measured and the mixture was cooled and discharged. Theresulting resinate could then be used in dispersion of pigments or inthe letting down of concentrated pigment pastes.

TABLE 1 Mass percent of total Component mixture Tall oil rosin 22.57 MO6fatty acid monomer 9.67 Maleic anhydride 2.77 Toluene 52.65 Water 0.12Calcium hydroxide 4.09 Toluene (in slurry) 7.98 Tall oil fatty acid 0.05Acetic acid 0.10

Example 2 Solution Resinate with 10 Percent of Acid from Monomer

A reaction vessel was charged with tall oil rosin and MO6 fatty acidmonomer at ambient temperature, and said mixture was melted by raisingits temperature to 170° C. Then, said reaction vessel was furthercharged with maleic anhydride, and the temperature was raised to 225° C.Said mixture was kept at 225° C. for 60 min, after which the mixture wascooled to about 160° C. The reaction vessel was charged with toluene,and the mixture temperature was adjusted to about 92° C. The reactionvessel was further charged with acetic acid and water, followed by aslurry of toluene, tall oil fatty acid and calcium hydroxide. Themixture was held at 92° C. for 30 minutes, and the mixture viscosity wasdetermined to be ‘Z5’ (by the Gardner Holdt Bubble method), while thesolids content of the mixture was 34.5%. The mixture was then dehydratedby heating to 115° C. for about 70 min. Percent composition (by mass) ofthe total reaction mixture is indicated in Table 2.

TABLE 2 Mass percent of total Component mixture Tall oil rosin 27.88 MO6fatty acid monomer 3.10 Maleic anhydride 2.66 Toluene 52.36 Water 0.12Calcium hydroxide 4.80 (97% in water) Toluene (in slurry) 8.95 Tall oilfatty acid 0.05 Acetic acid 0.10 (85% in water) Weight of total mixture:1146 grams

Example 3 Solution Resinate with 30 Percent of Acid from Monomer

A reaction vessel was charged with tall oil rosin and MO6 fatty acidmonomer at ambient temperature, and said mixture was melted by raisingits temperature to 170° C. The reaction vessel was then charged withmaleic anhydride, and the temperature was raised to 225° C. Said mixturewas kept at 225° C. for 60 min, after which the mixture was cooled toabout 150° C. The reaction vessel was charged with toluene, and themixture temperature was adjusted to about 92° C. The reaction vessel wascharged with acetic acid and water, followed by a slurry of toluene,tall oil fatty acid and calcium hydroxide. The mixture was held at 92°C. for 30 minutes, and the mixture viscosity was determined to be A1 (bythe Gardner Holdt Bubble method). The reaction vessel was then furthercharged with 3 grams calcium hydroxide (as a 40% solution in toluene).The mixture was held at 92° C. for 30 minutes, and the mixture viscositywas determined to be U (by the Gardner Holdt Bubble method). The mixturewas then dehydrated by heating to about 115° C. for about 2 h. Followingdehydration, the mixture viscosity was determined to be F+ (by theGardner Holdt Bubble method), while the solids content of the mixturewas 37.38%. The mixture was cooled to 50° C. and discharged. Percentcomposition (by mass) of the total reaction mixture (prior to thesupplementary charging of calcium hydroxide) is indicated in Table 3.

TABLE 3 Mass percent of total Component mixture Tall oil rosin 22.37 MO6fatty acid monomer 9.59 Maleic anhydride 2.74 Toluene 52.21 Water 0.12Calcium hydroxide 4.41 (97% in water) Toluene (in slurry) 8.42 Tall oilfatty acid 0.05 Acetic acid 0.10 (85% in water) Weight of total mixture:2500 grams

Example 4 Solution Resinate with 30 Percent of Acid from Monomer

A reaction vessel was charged with tall oil rosin and MO6 fatty acidmonomer at ambient temperature, and said mixture was melted by raisingits temperature to 170° C. The reaction vessel was charged with maleicanhydride, and the temperature was raised to 225° C. Said mixture waskept at 225° C. for 60 min, after which the mixture was cooled to 160°C. The reaction vessel was charged with toluene, and the mixturetemperature was cooled to 92° C. The reaction vessel was charged withacetic acid and water, followed by a slurry of toluene, tall oil fattyacid and calcium hydroxide. The mixture was held at 92° C. for 30minutes, and the mixture viscosity was determined to be B or C (by theGardner Holdt Bubble method), while the solids content of the mixturewas 51.50%. The reaction vessel was charged with 6 grams calciumhydroxide, the mixture was held at 92° C. for 30 minutes, and themixture viscosity was determined to be D (by the Gardner Holdt Bubblemethod), while the solids content of the mixture was 52.58%. Thereaction vessel was charged with 4 grams calcium hydroxide, the mixturewas held at 92° C. for 25 minutes, and the mixture viscosity wasdetermined to be F (by the Gardner Holdt Bubble method), while thesolids content of the mixture was 52.73%. The reaction vessel wascharged with 2 grams calcium hydroxide, the mixture was further held at92° C. for 30 minutes, and the mixture viscosity was determined to be Ior J (by the Gardner Holdt Bubble method). The reaction vessel was thenfurther charged with 3 grams calcium hydroxide, the mixture was furtherheld at 92° C. for 30 minutes, and the mixture viscosity was determinedto be U—(by the Gardner Holdt Bubble method). The mixture was dehydratedby heating to about 115° C. for about 100 min. Following dehydration,the mixture viscosity was determined to be Q—(by the Gardner HoldtBubble method), while the solids content of the mixture was 54.02%. Themixture was cooled and discharged, and the final mixture viscosity wasdetermined to be Q—(by the Gardner Holdt Bubble method), while thesolids content of the final mixture was 54.30%. Percent composition (bymass) of the total reaction mixture (prior to the supplementary chargingof calcium hydroxide) is indicated in Table 4.

TABLE 4 Mass percent of total Component mixture Tall oil rosin 35.57 MO6fatty acid monomer 15.24 Maleic anhydride 1.51 Toluene 33.12 Water 0.10Calcium hydroxide 5.12 (97% in water) Toluene (in slurry) 9.19 Tall oilfatty acid 0.08 Acetic acid 0.08 (85% in water)) Weight of totalmixture: 1992.66 grams

Comparative Example 5C Solution Resinate Depleted in Fatty Acid Monomer

A reaction mixture was prepared in a manner similar to that described inExample 1, with the omission of MO6 fatty acid monomer. Followingdehydration, the solids content of the mixture was 36.99%. Percentcomposition (by mass) of the total reaction mixture is indicated inTable 5.

TABLE 5 Mass percent of total Component mixture Tall oil rosin 31 Maleicanhydride 2.2 Toluene 56 Water 0.1 Calcium hydroxide 4 (97% in water)Toluene (in slurry) 5.7 Tall oil fatty acid 0.05 Weight of totalmixture: 3,000 grams Percent yield: 97.87

Examples 6-10 Properties of Varnish Containing Fatty Acid Monomer

In these examples, varnish samples comprising resinate containing up to30% of acid as MO6 fatty acid monomer were analyzed for viscosity andsolid content, and the properties of these samples were compared tothose of varnish samples comprising resinate devoid of MO6 fatty acidmonomer. Test findings are summarized in Table 6.

TABLE 6 Percent of acid as MO6 fatty acid Percent as Viscosity Ex.Resinate sample monomer solids (mPa · s) 6 MERIGRAL ™ HV 0 36.28 535.4 7 0% MO6 0 37.09 103.5 8 10% MO6 10 36.32 235.8 9 30% MO6 30 34.52 526.710 SYLVAPRINT ™ 0 36.12 217.4 GS62126 T37

Examples 11-15 Properties of Varnish at Constant Viscosity

In these examples, varnish samples comprising resinate containing up to30% of acid as MO6 fatty acid mommomer, were each adjusted to 1 dPa·sviscosity, and analyzed for various properties. The properties comparedto those of varnish samples devoid of MO6 fatty acid monomer. Testfindings are summarized in Table 7.

TABLE 7 Percent of acid as MO6 fatty Blocking Fingertip Resinate acidViscosity Percent Stals drying Ex. sample monomer (dPa · s) as solids(min) time (s) 11 MERIGRAL ™ 0 1 31.14 15-18 29 HV 12  0% MO6 0 1 34.4315-18 29 13 10% MO6 10 1 32.76 15-18 29 14 30% MO6 30 1 29.37 6-9 30 15SYLVAPRINT ™ 0 1 33.64 12-15 26 GS62126 T37

Examples 16-20 Diluting Curves of Varnish Containing Fatty Acid Monomer

In these examples, varnish samples comprising resinate containing up to30% of acid as MO6 fatty acid monomer were analyzed for viscosity usinga flow cup (recorded in seconds) as a function of solids content,compared to varnish samples devoid of MO6 fatty acid monomer. Testfindings are summarized in Table 8.

TABLE 8 DILUTION TIMES (s) Percent of acid as MO6 fatty acid Solid intoluene (wt %) Ex. Resinate sample monomer 36 34 32 30 28 26 24 22 20 1816 MERIGRAL ™ 0 466 198 105 54 34 27 23 22 — — HV 17  0% MO6 0 200  89 51 37 30 26 24 23 — — 18 10% MO6 10  — 406 159 84 50 36 29 25 23 22 1930% MO6 30  103  58  40 31 27 25 23 22 — — 20 SYLVAPRINT ™ 0 196  80  4230 25 23 22 — — — GS62126 T37

Examples 21-25 Solvent Retention of Varnish Containing Fatty AcidMonomer

In these examples, varnish samples comprising resinate containing up to30% of acid as MO6 fatty acid monomer were analyzed for solventretention as a function of time, compared to varnish samples devoid ofMO6 fatty acid monomer. Test findings are summarized in Table 9.

TABLE 9 Percent of acid as MO6 fatty Solvent retention (%) acid AfterAfter After Ex. Resinate sample monomer 2 h 4 h 7 h Average 21MERIGRAL ™ HV 0 9.73 8.96 8.51 9.07 22  0% MO6 0 7.09 6.18 5.52 6.26 2310% MO6 10 7.04 5.60 4.23 5.62 24 30% MO6 30 8.68 8.34 7.54 8.18 25SYLVAPRINT ™ 0 8.47 8.14 7.61 8.07 GS62126 T37

Examples 26-30 Properties of Ink Containing Fatty Acid Monomer

In these examples, ink samples (comprising 3% pigment, 17.43% tolueneand 67.57% let-down) at 30 seconds viscosity and further comprisingresinate containing up to 30% of acid as MO6 fatty acid monomer, wereanalyzed for various properties. The properties are compared to those ofvarnish samples devoid of MO6 fatty acid monomer. Test findings aresummarized in Table 10.

TABLE 10 Example 26 27 28 29 30 Resinate sample MERIGRAL ™ 0% MO6 10%MO6 30% MO6 SYLVAPRINT ™ HV GS62126 T37 Percent of acid as 0 0 10 30 0MO6 fatty acid monomer Solid content (%) 19.9 20.1 19.5 16.4 20.5 Gloss6μ on APCO 63.4% 63.5% 61.1% 57.1% 61.0% 2.2 Optical density 6μ 1.261.26 1.26 1.27 1.26 Opacity 3 3 2 1 3 (1 = most transparent) ‘Hotblocking’ 1 1 1 1 1 (1 = best) Penetration 3 2 1 3 4 (1 = best) Opticaldensity 20% 0.19 0.22 0.22 0.25 0.22 Optical density 40% 0.36 0.40 0.400.45 0.40 Optical density 60% 0.60 0.64 0.65 0.69 0.63 Optical density80% 0.86 0.94 0.90 0.99 0.85 Optical density 1.18 1.32 1.30 1.31 1.20100% Gloss on 100% 38.0 43.6 42.0 42.5 40.0 screen

Examples 31-35 Properties of Varnish Containing Fatty Acid Monomer

In these examples, varnish samples comprising resinate containing up to50% of acid as MO6 fatty acid monomer were analyzed for viscosity andsolid content. The properties are compared to those of varnish samplesdevoid of MO6 fatty acid monomer. Test findings are summarized in Table11.

TABLE 11 Percent of acid as MO6 fatty acid Percent as Viscosity Ex.Resinate sample monomer solids (mPa · s) 31 MERIGRAL ™ HV 0 37.86 636.432  0% MO6 0 37.98 624.4 33 30% MO6 30 38.49 130.0 34 50% MO6 50 35.50381.9 35 SYLVAPRINT ™ 0 36.82 617.3 GS62126 T37

Examples 36-40 Properties of Varnish at Constant Viscosity

In these examples, varnish samples comprising resinate containing up to50% of acid as MO6 fatty acid monomer, and at 1 dPa·s viscosity, wereanalyzed for various properties. The properties are compared to those ofvarnish samples devoid of MO6 fatty acid monomer. Test findings aresummarized in Table 12.

TABLE 12 Percent of acid as MO6 Blocking Fingertip Resinate fatty acidViscosity Percent as Stals drying Ex. sample monomer (dPa · s) solids(min) time (s) 36 MERIGRAL ™ HV 0 1 31.64 15-18 29 37  0% MO6 0 1 32.2212-15 28 38 30% MO6 30 1 35.48 6-9 29 39 50% MO6 50 1 29.51 >18 30 40SYLVAPRINT ™ 0 1 31.77 12-15 27 GS62126 T37

Examples 41-44 Diluting Curves of Varnish Containing Monomer Fatty Acid

In these examples, varnish samples comprising resinate containing up to50% of acid as MO6 fatty acid monomer were analyzed for dilution time asa function of solids content, compared to varnish samples devoid of MO6fatty acid monomer. Test findings are summarized in Table 13.

TABLE 13 DILUTION TIMES (s) Percent of acid as Resinate monomer Solid intoluene (wt %) Ex. sample fatty acid 38.5 38.0 37.9 35.5 35 33 31 29 2725 23 21 19 17 41 MERIGRAL ™ 0 — — 584 — 205 100 54 36 28 24 23 — — — HV42  0% MO6 0 — 637 — — 167  81 50 36 29 26 24 23 — — 43 30% MO6 30  100— — —  50  38 32 28 25 24 — — — — 44 50% MO6 50  — — — 301 — 152 104  5951 34 29 26 24 22

Examples 45-49 Solvent Retention of Varnish Containing Monomer FattyAcid

In these examples, varnish samples comprising resinate containing up to50% of acid as MO6 fatty acid monomer were analyzed for solventretention as a function of time, compared to varnish samples devoid ofMO6 fatty acid monomer. Test findings are summarized in Table 14.

TABLE 14 Percent of acid as Solvent retention (%) Resinate monomer AfterAfter After Ex. sample fatty acid 2 h 4 h 7 h Average 45 MERIGRAL ™ 09.76 9.27 8.77 9.27 HV 46  0% MO6 0 11.66 11.23 11.16 11.35 47 30% MO630 9.18 8.84 8.04 8.68 48 50% MO6 50 12.33 12.07 12.04 12.15 49SYLVAPRINT ™ 0 9.03 8.25 8.05 8.44 GS62126 T37

Examples 50-54 Properties of Ink Containing Monomer Fatty Acid

In these examples, ink samples (comprising 3% pigment, 21.72% tolueneand 63.28% let-down) at 30 seconds viscosity and further comprisingresinate containing up to 50% of acid as MO6 fatty acid monomer, wereanalyzed for various properties. These properties are compared to thoseof varnish samples devoid of MO6 fatty acid monomer. Test findings aresummarized in Table 15.

TABLE 15 Example 50 51 52 53 54 Resinate sample MERIGRAL ™ 0% MO6 30%MO6 50% MO6 SYLVAPRINT ™ HV GS62126 T37 Percent of acid 0 0 30 50 0 asmonomer fatty acid Solid content (%) 19.32 18.06 18.26 15.48 19.65 Gloss6μ on 62.3% 62.0% 57.0% 45.3% 60.0% APCO 2.2 Optical density 1.46 1.401.46 1.40 1.44 6μ Opacity 3 3 2 4 1 (1 = most transparent) ‘Hotblocking’, 1 1 1 1 1 one layer (1 = best) ‘Hot blocking’, 3 1 1 2 2 3layers (1 = best) Penetration 1 1 2 2 3 (1 = best) Optical density 0.190.18 0.24 0.24 0.21 20% Optical density 0.40 0.41 0.43 0.43 0.41 40%Optical density 0.64 0.68 0.67 0.68 0.67 60% Optical density 0.91 0.970.94 0.96 0.95 80% Optical density 1.29 1.34 1.29 1.36 1.33 100% Glosson 100% 39.7 42.5 40.5 34.5 41.2 screen

Example 55 Resinate with 30 Percent of Acid from Monomer, Prepared byFusion Method

A reaction vessel was charged with tall oil rosin (TOR), Chinese gumrosin and MO6 fatty acid monomer at ambient temperature, and the mixturewas melted by raising its temperature to about 175° C. The reactionvessel was then further charged with maleic anhydride, and the reactionmixture was heated to about 200° C. for about 30 minutes. The reactionmixture was then cooled to about 190° C. before the reaction vessel wasfurther charged slowly with a slurry of xylene, tall oil fatty acid(TOFA), calcium hydroxide and magnesium oxide. The reaction mixture wasthen heated to about 235° C. and the reaction vessel was further chargedwith acetic acid. The reaction mixture was heated to about 255° C. andanalyzed for acid number and viscosity. The reaction mixture was thenheld at about 255° C. for about 60 minutes more and analyzed again foracid number and viscosity. The reaction mixture was then held at about255° C. for about 130 minutes more and analyzed again for acid numberand viscosity. The reaction continued to be held at about 255° C. forseveral additional hours, and was analyzed for acid number and viscosityas deemed necessary. Percent composition (by mass) of the total reactionmixture, sample acid numbers, and sample viscosity measurements areindicated in Table 16.

TABLE 16 Mass percent of total Component mixture TOR 35.75 Chinese gumrosin 15.32 MO6 Monomer 22.16 Maleic anhydride 5.38 Ca(OH)₂ 5.29 (97% inwater) MgO 1.19 TOFA 0.23 Xylene (in slurry) 9.58 Xylene (wash) 4.56Acetic acid 0.55 (glacial) Weight of total mixture: 1096.50 gramsPercent yield 82.48 (theoretical) Percent of acid 25.6 equivalents fromMO6 Acid value Viscosity (g/mL KOH) (mPas) Sample #1: 92.07 14.2 Sample#2: 87.3 17 Sample #3: 69.46 18 Final sample: 68.8 24

Examples 56-64 Resinates with 30 Percent of Acid From Monomer, Preparedby Fusion Method

Resinates wherein about 30 wt % of the acidic components of the reactionmixture is derived from Monomer, were prepared in a manner similar tothat described in EXAMPLE 55. Percent composition (by mass) of the totalreaction mixture, sample acid numbers, and sample viscosity measurementsare indicated in Table 17.

TABLE 17 Example 56a 56b 57a 57b 58 59 60 61a 61b 62 63 64 ComponentMass percent of total mixture SYLVAROS ™ 85 34.14 34.14 14.63 14.63 — —— — — — — — tall oil rosin Chinese gum rosin 14.63 14.63 34.14 34.14 — —— — — — — — SYLVAROS ™ NCY — — — — 47.08 46.26 48.20 48.51 48.51 48.4148.68 48.54 tall oil rosin MO6 21.16 21.16 21.16 21.16 20.18 19.83 20.6620.79 20.79 20.75 20.73 20.80 Monomer Maleic anhydride 5.49 5.49 5.495.49 5.54 5.44 5.67 5.71 5.71 5.70 5.68 5.71 Ca(OH)₂ 5.92 5.92 5.92 5.926.59 6.91 6.21 6.09 6.09 6.18 6.06 6.05 (97% in water) MgO 1.33 1.331.33 1.33 1.49 1.56 1.40 1.37 1.37 1.38 1.35 1.36 TOFA 0.22 0.22 0.220.22 0.22 0.22 0.23 0.23 0.23 0.23 0.27 0.23 Xylene (in slurry) 10.8910.89 10.89 10.89 12.13 12.70 11.61 11.23 11.23 11.30 11.18 11.15 Xylene(wash) 5.66 5.66 5.66 5.66 6.15 6.48 5.40 5.44 5.44 5.42 5.41 5.53Acetic acid 0.57 0.57 0.57 0.57 0.62 0.60 0.63 0.63 0.63 0.63 0.63 0.63(glacial) Total mixture 1148.25 1148.25 1148.25 1148.25 1137.50 1157.501111.00 1103.85 1103.85 1106.15 1109.25 1103.25 weight (grams) Percentyield 79.69 79.69 79.69 79.69 77.22 76.13 78.77 79.19 79.19 79.08 79.2979.21 (theoretical) Percent of acid 24.9 24.9 24.6 24.6 18.9 18.9 18.918.9 18.9 18.9 19.0 18.9 equivalents from MO6 Final acid value (g/mL 7159.18 63.4 55.3 64.9 — 76.25 66.72 74.78 64.9 — 71.25 KOH) Sample 1viscosity — — — — 118 — 48 31.3 — 42.5 — 33.6 (mPas) Sample 2 viscosity— — — — — — 525 100.7 — 102 — 118.5 (mPas) Final viscosity 214 243 72 *1300 — 105 507 190 1570 — 345 (mPas) *Too viscous to be measured

Examples 65-67 Resinates with 30 Percent of Acid from Monomer, Preparedby Fusion Method

Resinates wherein about 30 wt % of the acidic components of the reactionmixture is derived from Monomer, were prepared in a manner similar tothat described in EXAMPLE 55, substituting HRJ1367 phenolic resin forthe maleic anhydride. Percent composition (by mass) of the totalreaction mixture, sample acid numbers, and sample viscosity measurementsare indicated in Table 18.

TABLE 18 Example 65 66 67 Component Mass percent of total mixture TOR16.20 15.82 15.38 Chinese gum rosin 37.79 36.92 35.89 MO6 23.14 22.6021.97 Monomer HRJ 1367 3.32 3.01 3.00 phenolic resin Ca(OH)₂ 5.83 6.507.17 (97% in water) Xylene (in slurry) 8.75 9.74 10.75 Xylene (wash)3.94 4.38 4.84 Acetic acid 1.05 1.02 1.00 (80%) Total mixture 1234.931264.00 1300.24 weight (grams) Percent yield 84.04 82.29 80.53(theoretical) Percent of acid 30.2 30.2 30.2 equivalents from MO6 Finalacid value 61 51 36 (g/mL KOH) Final viscosity 14.0 14.0 49.4 (mPas)Final appearance Clear Clear Slightly hazy

Examples 68-70 Resinates with 20 Percent of Acid from Monomer, by FusionMethod

Resinates wherein about 20 wt % of the acidic components of the reactionmixture is derived from Monomer, were prepared in a manner similar tothat described in EXAMPLE 55 and EXAMPLES 65-67. Percent composition (bymass) of the total reaction mixture, acid numbers, and viscositymeasurements are indicated in Table 19.

TABLE 19 Example 68 69 70 Component Mass percent of total mixture TOR16.77 18.04 17.81 Chinese gum rosin 39.19 42.10 41.55 MO6 13.93 15.0414.84 Monomer Maleic anhydride 5.49 — — HRJ 1367 — 3.02 2.98 phenolicresin Ca(OH)₂ 5.92 6.50 6.82 (97% in water) MgO — — — TOFA — — — Xylene(in slurry) 10.89 9.74 10.24 Xylene (wash) 5.66 4.38 4.61 Acetic acid0.57 1.17 1.15 (glacial) (80%) (80%) Total mixture 1400.00 1108.381123.15 weight (grams) Percent yield 80.04 82.22 81.35 (theoretical)Percent of acid 15.0 20.1 20.1 equivalents from MO6 Final acid value60.7 42 39 (g/mL KOH) Final viscosity 237.0 16.8 13.0 (mPas) Finalappearance — Clear Clear

Examples 71-74 Resinates with 10-15 Percent of Acid from Monomer,Prepared by Fusion Method

Resinates wherein about 10-15 wt % of the acidic components of thereaction mixture is derived from Monomer, were prepared in a mannersimilar to that described in EXAMPLE 55 and EXAMPLES 65-67. Percentcomposition (by mass) of the total reaction mixture, sample acidnumbers, and sample viscosity measurements are indicated in Table 20.

TABLE 20 Example 71 72 73 74 Component Mass percent of total mixture TOR18.71 20.29 19.18 19.15 Chinese gum rosin 43.72 47.34 44.76 44.69 MO67.89 7.51 11.28 11.27 Monomer Maleic anhydride 6.12 — — — HRJ 1367 —2.99 2.97 2.97 phenolic resin Ca(OH)₂ 5.74 6.47 6.47 6.46 (97% in water)MgO 1.29 — — — TOFA 0.20 — — — Xylene (in slurry) 10.53 9.71 9.71 9.70Xylene (wash) 5.18 4.37 4.37 4.36 Acetic acid 0.63 1.31 1.24 1.40(glacial) (80%) (80%) (80%) Total mixture 1255.10 985.76 1042.58 4176.78weight (grams) Percent yield (theoretical) 81.05 82.20 82.24 82.23Percent of acid equivalents 7.6 10.0 15.1 15.1 from MO6 Final acid value62.7 48 47 45 (g/mL KOH) Final viscosity 125.0 13 13 20 (mPas) Finalappearance — Clear Clear Clear

Examples 75-80 Resinates with 50 Percent of Acid from Monomer, Preparedby Fusion Method

Resinates wherein about 50 wt % of the acidic components of the reactionmixture is derived from Monomer, were prepared in a manner similar tothat described in EXAMPLE 55. Percent composition (by mass) of the totalreaction mixture, sample acid numbers, and sample viscosity measurementsare indicated in Table 21.

TABLE 21 Example 75 76 77 78 79a 79b 80 Component Mass percent of totalmixture TOR 32.66 34.52 33.88 34.97 35.14 35.14 — Chinese gum rosin — —— — — — 37.90 MO6 32.66 34.52 33.88 34.97 35.14 35.14 37.90 MonomerMaleic anhydride 5.26 5.25 5.24 5.32 5.34 5.34 5.76 Ca(OH)₂ 7.23 6.466.64 6.23 6.08 6.08 4.12 (97% in water) MgO 1.64 1.45 1.50 1.40 1.361.36 1.19 TOFA 0.25 0.21 0.20 0.21 0.21 0.21 0.23 Xylene (in slurry)13.31 11.91 12.15 11.40 11.19 11.19 8.05 Xylene (wash) 6.57 5.25 6.085.06 5.09 5.09 4.12 Acetic acid 0.42 0.44 0.44 0.45 0.45 0.45 0.72(glacial) Total mixture 1217.10 1200.32 1201.45 1184.70 1179.15 1179.151093.02 weight (grams) Percent yield 75.47 78.69 77.50 79.55 79.83 79.8385.74 (theoretical) Percent of acid 32.7 33.3 33.1 33.3 33.3 33.3 49.2equivalents from MO6 Final acid value 68.89 67.43 77.00 63.87 78.4080.10 100.7 (g/mL KOH) Sample 1 viscosity — — — — — 76 — (mPas) Sample 2viscosity — — — — — 100 — (mPas) Final viscosity * 503 * 98.7 314235 >20 (mPas) *Too viscous to be measured.

Examples 81C-90C(Comparative) Resinates with no Monomer, Prepared byFusion Method

Resinates wherein essentially none of the acidic components of thereaction mixture are derived from Monomer, were prepared in a mannersimilar to that described in EXAMPLE 55 and EXAMPLES 65-67. Percentcomposition (by mass) of the total reaction mixture, sample acidnumbers, and sample viscosity measurements are indicated in Table 22.

TABLE 22 Example 81C 82C 83C 84C 85C 86C 87C 88C 89C 90C Component Masspercent of total mixture TOR 69.44 72.67 71.30 49.85 80.33 81.52 80.6423.15 23.56 23.99 Chinese gum rosin — — — 21.36 — — — 54.03 54.99 55.97Maleic anhydride 5.25 5.50 5.50 5.49 — — — — — — HRJ 1367 — — — — 3.343.00 3.00 3.00 3.00 2.97 phenolic resin Ca(OH)₂ 6.32 5.40 5.82 5.68 4.774.50 4.79 5.86 5.44 5.59 (97% in water) MgO 1.42 1.21 1.30 1.28 — — — —— — TOFA 0.20 0.22 0.23 0.23 — 0.25 0.25 0.26 0.26 0.25 Xylene (inslurry) 11.57 9.78 10.62 10.43 7.23 6.80 7.18 8.79 8.20 7.12 Xylene(wash) 5.34 4.66 4.66 5.12 3.40 3.00 3.21 3.96 3.58 3.19 Acetic acid0.45 0.56 0.56 0.56 0.94 0.94 0.94 0.95 0.97 0.93 (glacial) (glacial)(glacial) (glacial) (80%) (80%) (80%) (80%) (80%) (80%) Total mixture1123.30 1073.40 1073.00 1400.00 1000.00 1000.00 1400.00 1364.95 1341.251412.00 weight (grams) Percent yield (theoretical) 78.32 81.38 80.2880.54 85.33 86.26 85.55 83.84 84.99 86.39 Final acid value 57.3 63.8 5854.7 — — — 53 68 — (g/mL KOH) Final viscosity 324 85 214 52 — 14 16 2016 — (mPas) Final appearance — — — — — — — Hazy Clear —

Examples 91C-92C (Comparative) Resinates with no Monomer, Prepared byFusion Method

Resinates wherein essentially none of the acidic components of thereaction mixture are derived from Monomer, were prepared in a mannersimilar to that described in EXAMPLE 55. Percent composition (by mass)of the total reaction mixture, sample acid numbers, and sample viscositymeasurements are indicated in Table 23.

TABLE 23 Example 91C 92C Mass percent of total Component mixture TOR85.66 86.66 Octyl phenol 3.09 — Bisphenol A 0.91 — p-tert-Butylphenol —2.88 Paraformaldeyhde (91%) 1.91 1.93 Ca(OH)₂ 5.08 5.14 (97% in water)Acetic acid 3.36 3.40 (80%) Total mixture 1102.74 1090.10 weight (grams)Percent yield (theoretical) 94.01 93.94

Examples 93C, 94-95, 96C-97C Properties of Ink Formulations ContainingMonomer

In these examples, samples of ink formulations comprising resinatecontaining up to 30% of acid as MO6 Monomer were analyzed for viscosityand solid content, and the properties of these samples were compared tothose of ink formulation samples comprising resinate devoid of MO6Monomer. Test findings are summarized in Table 24.

TABLE 24 Percent of acid as MO6 fatty acid Percent as Viscosity Ex.Resinate sample monomer solids (mPa · s) 93C SYLVAPRINT ™ 0 44.02 2143874 94 11% MO6 11 46.98 128 95 30% MO6 30 44.81 230 96C  0% MO6 0 42.92114 97C  0% MO6 0 40.34 128

Examples 98C, 99-100, 101C-102C Solvent Retention of Ink FormulationsContaining Monomer

In these examples, samples of ink formulations comprising resinatecontaining up to 30% of acid as MO6 Monomer were analyzed for solventretention as a function of time, compared to ink formulation samplesdevoid of MO6 Monomer. Of the samples tested, those containing Monomerwere determined to have the least solvent retention, and therefore thebest ink-drying properties. Test findings are summarized in Table 25.

TABLE 25 Percent of acid Solvent retention (%) as MO6 fatty After AfterAfter Aver- Ex. Resinate sample acid monomer 2 h 4 h 7 h age  98CSYLVAPRINT ™ 0 16.26 15.50 13.94 15.23 3874  99 11% MO6 11 7.13 6.476.40 6.67 100 30% MO6 30 8.70 7.44 7.11 7.75 101C  0% MO6 0 13.80 12.6711.55 12.67 102C  0% MO6 0 11.28 10.78 10.65 10.90

Examples 103C, 104-105, 106C-107C Properties of Ink Containing Monomer

In these examples, ink samples (comprising 3% pigment, toluene andlet-down as indicated) at 30 seconds viscosity and further comprisingresinate containing up to 30% of acid as MO6 Monomer, were analyzed forvarious properties. The properties are compared to those of ink samplesdevoid of MO6 Monomer. Test findings are summarized in Table 26.

TABLE 26 Example 103C 104 105 106C 107C Resinate sample SYLVAPRINT ™ 11%MO6 30% 0% 0% MO6 3874 MO6 MO6 Percent of acid as MO6 0 11 30 0 0 fattyacid monomer Toluene (wt %) 4.22 6.47 5.25 4.92 6.16 Let-down (wt %)80.78 78.53 79.75 80.08 78.84 Solid content (%) 21.77 21.74 21.62 21.6621.04 Gloss 6μ on APCO 2.2 76 74 76 75 78 Optical density 6μ 1.28 1.221.26 1.24 1.27 ‘Hot blocking’ 12μ 4 3 2 1 5 (1 = best)* Optical density20% 0.24 .024 .025 .024 .025 Optical density 40% 0.43 0.42 0.43 0.410.43 Optical density 60% 0.64 0.63 0.65 0.62 0.64 Optical density 80%0.87 0.87 0.87 0.86 0.87 Optical density 100% 1.27 1.27 1.27 1.28 1.28Gloss on 100% screen 52.0 48.6 46 46.8 44.9 *After application, printwas immediately put in heat sealer (without drying).

All of the above U.S. patents, U.S. patent application publications,U.S. patent applications, foreign patents, foreign patent applicationsand non-patent publications referred to in this specification and/orlisted in the Application Data Sheet, are incorporated herein byreference, in their entirety.

From the foregoing it will be appreciated that, although specificembodiments of the invention have been described herein for purposes ofillustration, various modifications may be made without deviating fromthe spirit and scope of the invention. Accordingly, the invention is notlimited except as by the appended claims.

1. A resinate composition comprising the reaction product of reactants,the reactants comprising: (a) at least one rosin selected from the groupconsisting of wood rosin, gum rosin, and tall oil rosin; (b) Monomer,and (c) metal salt, the metal salt comprising a metal cation, the metalselected from Group IIA or Group IIB metals of the Periodic Table. 2.The composition of claim 1 wherein the metal is selected from the groupconsisting of zinc, magnesium, calcium, and mixtures thereof.
 3. Thecomposition of claim 1 wherein the metal salt comprises an anionselected from the group consisting of acetate, carbonate, bicarbonate,formate, hydroxide, oxalate, oxide, and mixtures thereof.
 4. Thecomposition of claim 1 wherein the reactants further compriseα,β-unsaturated carboxylic compound, tall oil fatty acid, or acombination thereof wherein the α,β-unsaturated carboxylic compound isselected from the group consisting of maleic anhydride, fumaric acid,mono (C₁-C₁₂) ester of fumaric acid, di(C₁-C₁₂ alkyl) ester of fumaricacid, acrylic acid, C₁-C₁₂ alkyl ester of acrylic acid, methacrylicacid, C₁-C₁₂ alkyl ester of methacrylic acid, itaconic acid, C₁-C₁₂alkyl ester of itaconic acid, and mixtures thereof.
 5. The compositionof claim 1, comprising up to about 80 wt % solvent, based on the totalweight of the composition.
 6. The composition of claim 1, wherein thesolvent is selected from the group consisting of lower organic acid,hydrocarbon, water, and mixtures thereof.
 7. The composition of claim 1,wherein the solvent is composed of about 70-100 wt % hydrocarbon, up toabout 15 wt % lower organic acid, and optionally up to about 15 wt %water.
 8. The composition of claim 1 wherein the reactants furthercomprise a reactant selected from the group consisting of phenol,aldehyde, and phenolic resin, and the reactants comprise 0-10 wt %α,β-unsaturated carboxylic compound.
 9. The composition of claim 8wherein the reactants comprise 0-2 wt % α,β-unsaturated carboxyliccompound and the metal comprises calcium.
 10. The composition of claim 1wherein the reactants comprise α,β-unsaturated carboxylic compound, andthe composition contains 0-10 wt % solvent.
 11. The composition of claim10 wherein the reactants comprise calcium and zinc salts, and thecomposition contains 0-5 wt % solvent.
 12. A process for preparing aresinate composition comprising the steps of (a) melting at least onerosin selected from the group consisting of wood rosin, gum rosin, andtall oil rosin in a reaction vessel, optionally in admixture withMonomer; (b) charging the reaction vessel with Monomer if Monomer is notalready present in the reaction vessel; (c) charging the reaction vesselwith a metal salt comprising a cation selected from Group IIA or GroupIIB of the Periodic Table, and optionally solvent, to provide a reactionmixture; (d) incubating the reaction mixture at elevated temperature toproduce a reaction product; and (e) cooling the reaction product (e) toyield a resinate composition.
 13. The process of claim 12 wherein thereactants comprise acid equivalents attributed to fatty acid and acidequivalents attributed to rosin, and Monomer contributes about 55-1% ofthe total acid equivalents attributed to rosin and fatty acid.
 14. Theprocess of claim 12 wherein the reactants comprise acid equivalentsattributed to Monomer and acid equivalents attributed to rosin, and theratio of acid equivalents attributed to rosin:acid equivalentsattributed to Monomer is in the range of about 0.5:1 to 15:1.
 15. Theprocess of claim 12 wherein the cation of the metal salt is selectedfrom the group consisting of a cation of zinc, magnesium, calcium, andmixtures thereof.
 16. The process of claim 12 wherein the anion of themetal salt is selected from the group consisting of acetate, carbonate,bicarbonate, formate, hydroxide, oxalate, oxide, and mixtures thereof.17. The process of claim 12 wherein the solvent is selected from one ora combination of an inorganic solvent and an organic solvent, whereinthe organic solvent does not contain a hydroxyl, aldehyde, alkenyl,cycloalkenyl, or nitrogen-containing group.
 18. The process of claim 17wherein the solvent is selected from the group consisting of lowerorganic acid, hydrocarbon, water, and mixtures thereof.
 19. The processof claim 17 wherein the solvent comprises about 70-100 wt % hydrocarbon,up to about 15 wt % lower organic acid, and 0-15 wt % water.
 20. Theprocess of claim 12 further including the step of heating the reactionproduct to evaporate excess solvent.
 21. The process of claim 12,further comprising at least one step selected from (a) addingα,β-unsaturated carboxylic compound to the reaction vessel after rosinmelting and prior to incubation; or (b) charging the reaction vesselwith tall oil fatty acid after rosin melting and prior to incubation.22. The process of claim 12 wherein maleic anhydride is added to thereaction vessel.
 23. The process of claim 12 further comprising (a)charging the reaction vessel with a phenolic compound; and (b) chargingthe reaction vessel with formaldehyde or a reactive equivalent thereof.24. The process of claim 12 further comprising charging the reactionvessel with polyhydric alcohol.
 25. The process of claim 12 comprisingthe ordered steps of (a) melting the rosin in a reaction vessel at about170° C., optionally in admixture with Monomer; (b) charging the reactionvessel with Monomer if Monomer is not already present in the reactionvessel; (c) heating the reaction mixture at about 225° C. for about 1hour; (d) cooling the reaction mixture to less than about 100° C.; (e)charging the reaction vessel with one or more of lower organic acid,water and hydrocarbon; (f) charging the reaction vessel with a slurrycomprising hydrocarbon solvent and alkaline metal salt; (g) incubatingthe reaction mixture at less than about 100° C. for about 30 minutes;and (h) heating the reaction mixture at about 115° C. for about 1-2hours before cooling and discharging said reaction mixture.
 26. Theprocess of claim 12 wherein the resinate composition is prepared by afusion method and comprises (a) melting the rosin in a reaction vesselat about 170° C., optionally in admixture with Monomer; (b) charging thereaction vessel with Monomer if Monomer is not already present in thereaction vessel; (c) heating the reaction mixture at about 200° C. forabout 1 hour; (d) charging the reaction vessel with a slurry comprisinghydrocarbon solvent and alkaline metal salt; (e) incubating the reactionmixture about 250° C. for about 90 minutes; (f) charging the reactionvessel with lower organic acid; (g) further incubating the reactionmixture for about 1 hour before cooling and discharging the finalreaction mixture.
 27. The process of claim 26 wherein the reactionvessel is charged with about 20-85 wt % rosin, about 1-50 wt % Monomer,about 1-15 wt % alkaline metal salt, up to about 30 wt % hydrocarbonsolvent, up to about 5 wt % lower organic acid, α,β-unsaturatedcarboxylic compound representing about 1-25 wt % of the reactants, and0-5 wt % water.
 28. The process of claim 26, wherein the slurry furthercomprises tall oil fatty acid representing up to about 2 wt % of thefinal reaction mixture.